CN103602355A - Fuel additives for treating internal deposits of fuel injectors - Google Patents

Abstract

Provided are fuel additives for treating internal deposits of fuel injectors. A method for cleaning internal components of a fuel injector for a diesel engine, includes operating a fuel injected diesel engine on a fuel composition comprising a major amount of fuel and from about 10 to about 100 ppm by weight based on the total weight of the fuel composition of (A) a compound of the formula: and tautomers and enantiomers thereof, wherein R2 is a hydrocarbyl group having a number average molecular weight ranging from 100 to 5000.

Description

Fuel dope for the treatment of the inside deposition thing of fuel injector

related application

The application is that the part of the present co-pending application sequence number 12/119,788 of submission on May 13rd, 2008 continues, and is the part continuation of the present co-pending application sequence number 13/111.364 of submission on May 19th, 2011.

Technical field

The disclosure relates to some diesel fuel additive, and relates to the method that cleans and/or prevent at the inside deposition thing of the injector for diesel oil fuel operation engine.Specifically, the disclosure relates to effective antagonism in the method for the inside deposition thing of the injector of the engine for ultra-low-sulphur diesel operating fuel.

Background technology

The nearest variation of diesel oil fuel and diesel fuel additive has produced the relevant new injector performance problem of settling, comprises the utilization novel type settling that early diesel oil fuel preparation does not live through.Injector performance problem is crossed over all links; Fleet, winning equipment, tillage equipment, railway and inland shipping engine on road.

Vehicles operator, fuel marketing personnel and manufacturers of engines are now just witnessed the settling forming on the internal part of fuel injector.If do not processed, these settlings just can cause remarkable power loss, reduce fuel economy, increase fault-time and produce higher maintenance cost owing to changing too early " adhesion (stuck) injector " under extreme case.Believe that new settling is that other that use in some common corrosion inhibitor, biofuel component and acid friction modifiers or fuel reacts with micro-transition metal, alkali and alkaline earth metal ions containing carboxyl group, is created in ultra-low-sulphur diesel (ULSD) fuel than in the past compared with being more difficult for the result of molten salt in high-sulfur fuel.When the fuel for high-pressure common rail (HPCR) engine design exists this type of salt, salt can tend to be deposited on the very close tolerance region (very tight tolerance area) of injector.This type of settling can cause bad fuel injection, and bad fuel injection can cause power loss then, loses fuel economy, not smooth running engine, and finally cause too much vehicle break-down time and maintenance cost.

ULSD be equivalent to now distillate fuel in U.S. supply all approximately 79%.Recyclable fuel standard minimum quantity for biofuel was also increased to 1,000,000,000 gallons in 2012.There are indications, in fuel, use the amount of required biofuel higher in the future.Therefore, the fuel nomination list of variation continues to shift to more biofuel (producing the possible Sediment Source of another kind of material in fuel system) in more ULSD (having less solvability for the salt that can generate) and market.

Summary of the invention

According to the disclosure, exemplary provides a kind of method cleaning for the intraware of the fuel injector of diesel motor.Method comprises with a kind of fuel composition operation fuel injection diesel motor, the fuel that described fuel composition comprises main amount and the compound to (A) following formula of about 100ppm weight based on fuel composition gross weight approximately 10:

And tautomer and enantiomer, wherein R ²for thering is the alkyl of 100 to 5000 daltons number average molecular weight.

Another embodiment of the present disclosure provides the method for the amount of the salt deposit of a kind of minimizing on the intraware of the fuel injector for fuel injection diesel motor.Method comprises with a kind of fuel composition operation diesel motor, the compound of (A) following formula of the fuel that described fuel composition comprises main amount and minor amount:

And tautomer and enantiomer, wherein R ²for thering is the alkyl of 100 to 5000 daltons number average molecular weight.

Another embodiment of the present disclosure provides a kind of method that prevents that the fuel filter for the fuel injector of fuel injection diesel motor from stopping up.Method comprises provides (A) of the fuel of main amount and the minor amount compound of following formula:

And tautomer and enantiomer, wherein R ²for thering is the alkyl of 100 to 5000 daltons number average molecular weight, and (B) a certain amount of hydrocarbyl succinic imide dispersion agent; Wherein in fuel, the weight ratio of A:B is 1:2 to 1:10; And make fuel flow pass through the fuel filter for fuel injector.

The advantage of fuel dope described herein is, additive can not only reduce the amount of the inside deposition thing forming in direct and/or indirect diesel fuel injectors, and additive also can effectively clean dirty fuel injector, and can prevent the obstruction of fuel filter in the supply of fuel of fuel injector.

Other embodiments of the present disclosure and advantage can part be set forth in the following discussion, and/or can be familiar with by implementing the disclosure.Should be appreciated that, aforementioned general description and following detailed description are all only exemplary and illustrative, are not to restriction of the present disclosure as required for protection.

Particularly, the disclosure relates to following embodiment:

1. the method cleaning for the intraware of the fuel injector of diesel motor, described method comprises with a kind of fuel composition operation fuel injection diesel motor, the fuel that described fuel composition comprises main amount and the compound to (A) following formula of about 500ppm weight based on fuel composition gross weight approximately 10:

And tautomer and enantiomer, wherein R ²for thering is the alkyl of 100 to 5000 daltons number average molecular weight.

2. the method for clause 1, wherein R ²for thering are approximately 200 polyisobutene to approximately 3,000 daltons number average molecular weight.

3. the method for clause 1, wherein fuel injection diesel motor comprises that direct fuel sprays diesel motor.

4. the method for clause 1, further comprises (B) a certain amount of hydrocarbyl succinic imide dispersion agent, and wherein in fuel, the weight ratio of A:B is 1:2 to 1:10.

5. the method for clause 4, the reaction product that wherein hydrocarbyl succinic imide dispersion agent comprises polyalkenyl amber acid or anhydride and tetren.

6. the method for clause 5, wherein polyalkenyl amber acid or anhydride is derived from the polyisobutene with 800 to 1100 daltons number average molecular weight.

7. the method for clause 6, wherein polyisobutene comprises the highly reactive polyisobutenes with at least 70% weight or more end olefinic double bonds.

8. the method for clause 4, wherein fuel package is containing 50 to the 500ppm A of weight and the mixture of B.

9. the method for the amount of the minimizing salt deposit on the intraware of the fuel injector for fuel injection diesel motor, described method comprises with a kind of fuel composition operation diesel motor, the compound of (A) following formula of the fuel that described fuel composition comprises main amount and minor amount:

And tautomer and enantiomer, wherein R ²for thering is the alkyl of 100 to 5000 number-average molecular weights.

10. the method for clause 9, wherein fuel package is containing based on fuel composition gross weight approximately 10 compounds to about 100ppm weight (A).

The method of 11. clauses 9, wherein R ²for thering are approximately 200 alkyl to approximately 3000 daltons number average molecular weight.

The method of 12. clauses 9, wherein fuel injection diesel motor is that direct fuel sprays diesel motor.

The method of 13. clauses 9, wherein fuel is ultra-low-sulphur diesel fuel.

The method of 14. clauses 9, further comprises (B) a certain amount of hydrocarbyl succinic imide dispersion agent, and wherein in fuel, the weight ratio of A:B is 1:2 to 1:10.

The method of 15. clauses 14, the reaction product that wherein hydrocarbyl succinic imide dispersion agent comprises polyalkenyl amber acid or anhydride and tetren.

The method of 16. clauses 15, wherein polyalkenyl amber acid or anhydride is derived from the polyisobutene with 800 to 1100 daltons number average molecular weight.

The method of 17. clauses 16, wherein polyisobutene comprises the highly reactive polyisobutenes with at least 70% weight or more end olefinic double bonds.

The method of 18. clauses 14, wherein fuel package is containing 50 to the 500ppm A of weight and the mixture of B.

19. 1 kinds of methods that prevent that the fuel filter for the fuel injector of fuel injection diesel motor from stopping up, described method comprises following (A) and the mixture (B) that the fuel of main amount and minor amount are provided: (A) compound of following formula

And tautomer and enantiomer, wherein R ²for thering is the alkyl of 100 to 5000 daltons number average molecular weight; (B) a certain amount of hydrocarbyl succinic imide dispersion agent; Wherein in fuel, the weight ratio of A:B is 1:2 to 1:10; And

Make fuel flow pass through the fuel filter for fuel injector.

The method of 20. clauses 19, wherein fuel filter has 2 microns of holes for fuel flow.

The method of 21. clauses 19, wherein fuel package is containing compound (the A)/Kg fuel to about 200mg based on the about 5mg of active benchmark.

The method of 22. clauses 19, wherein fuel package contains about 20mg to compound (A)/Kg fuel of about 120mg.

The method of 23. clauses 19, wherein fuel package is containing ultra-low-sulphur diesel (ULSD) fuel.

Accompanying drawing explanation

The graphic representation that Fig. 1 is the exhaust casing temperature of passing in time during on-test at fuel dope for four cylinder diesel motors.

Fig. 2 is not for being used the graphic representation of the exhaust casing temperature of passing in time after test in 8 hours of fuel sanitising agent for four cylinder diesel motors.

Fig. 3 and 4 is for being used the graphic representation (prior art) of the exhaust casing temperature that conventional oil sanitising agents pass in time for four cylinder diesel motors.

Fig. 5 and 6 is for being used the graphic representation of the exhaust casing temperature that the fuel sanitising agent of embodiment of the present disclosure passes in time for four cylinder diesel motors.

Fig. 7 is the graphic representation for the exhaust casing temperature of passing in time of the clean dirty fuel injector of fuel sanitising agent of a four cylinder used for diesel engine embodiment of the present disclosure.

Specific embodiments

Composition of the present disclosure (A) can minor amount be used for the diesel oil fuel of main amount, and can pass through amine compound or its salt of following formula

(alkyl that wherein R is selected from hydrogen and comprises approximately 1 to approximately 15 carbon atom, R ¹be selected from hydrogen and the alkyl that comprises approximately 1 to approximately 20 carbon atom) with the hydrocarbyl oxycarbonyl based compound of following formula

(R wherein ²for thering are approximately 200 alkyl to approximately 3000 daltons number average molecular weight) react and prepare.Do not expect to be subject to theoretical effects limit, the reaction product of believing amine and hydrocarbyl oxycarbonyl based compound is aminotriazole, for example the bis-amino triazole compounds of following formula

Comprise and there are approximately 200 tautomers to approximately 3000 daltons number average molecular weight.The five-ring of triazole is thought to aromatics.Aminotriazole is to oxygenant quite stable, and utmost point hydrolysis.Although uncertain, believe reaction product be polyalkenyl two-3-amino-1,2,4-triazole.

Term used herein " alkyl " is used with general significance well known to those skilled in the art.Specifically, " alkyl " refers to a kind of group, has the carbon atom that is directly connected to molecule rest part, and has dominant hydrocarbon character.The example of alkyl comprises:

(1) hydrocarbon substituent, aliphatic series (for example alkyl or alkenyl), alicyclic (for example cycloalkyl, cycloalkenyl group) substituting group, and aromatics-, the aromatic substituent of aliphatic series-and alicyclic-replace, and wherein encircle the cyclic substituents (for example, two substituting groups form alicyclic group together) that the another part by molecule completes;

(2) substituted hydrocarbon substituent, contain the substituting group of non-hydrocarbyl group, under this specification sheets linguistic context, this non-hydrocarbyl group does not change dominant hydrocarbon substituent (for example halogeno-group (especially chloro and fluoro), hydroxyl, alkoxyl group, sulfydryl, alkylthio, nitro, nitroso-group and sulphur oxygen base (sulfoxy));

(3) assorted substituting group, that is, when thering is main dominant hydrocarbon character, under this specification sheets linguistic context, otherwise the substituting group of the atom beyond carbon containing in the ring that formed by carbon atom or chain.Heteroatoms comprises sulphur, oxygen, nitrogen, and relates to for example substituting group of pyridyl, furyl, thienyl and imidazolyl.General in alkyl, for every 10 carbon atoms, there are no more than two or as other example, have the non-hydrocarbon substituent of no more than; In some embodiments, in alkyl, there is no non-hydrocarbon substituent.

Should be understood that " biological recyclable fuel " used herein and " biodiesel fuel " refer to any fuel obtaining from oil resource in addition.These resources include but not limited to cereal, corn, beans and other farm crop; Grass, for example switchgrass, awns belong to and hybrid grass; Algae, sea grass, vegetables oil; Natural fat; And composition thereof.In one aspect, biological recyclable fuel can comprise single hydroxyl alcohol, for example, comprise those alcohol of 1 to approximately 5 carbon atom.The unrestricted example of applicable single hydroxyl alcohol comprises methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol and primary isoamyl alcohol.

Should be understood that term used herein " mainly amount " refers to the amount that is more than or equal to 50% weight with respect to the gross weight of composition, for example approximately 80 to approximately 98% weight.Should be understood that in addition term used herein " minor amount " refers to the amount that is less than 50% weight with respect to the gross weight of composition.

Should be understood that term used herein " salt or salt deposit " refers to metal carboxylate.

amine compound

The applicable amine compound of following formula

Can be selected from guanidine and aminoguanidine or its salt, wherein R and R ¹be defined as above.Therefore, amine compound can be selected from the inorganic salt of guanidine, for example the halogenide of guanidine, carbonate, nitrate, phosphoric acid salt and orthophosphoric acid salt.Term " guanidine " refers to guanidine and guanidine derivative, for example aminoguanidine.In one embodiment, the guanidine compound for the preparation of additive is aminoguanidine bicarbonate.Aminoguanidine bicarbonate can be easy to obtain from commercial sources, or can well-known way preparation.

hydrocarbyl oxycarbonyl based compound

The hydrocarbyl oxycarbonyl radical reaction immunomodulator compounds of additive can be for having hydrocarbyl portion and carbonyl moiety and can being combined into amine compound any suitable combination thing of additive of the present disclosure.The unrestricted example of applicable hydrocarbyl oxycarbonyl based compound includes but not limited to succinyl oxide, the succsinic acid of alkyl replacement and the ester of the succsinic acid that alkyl replaces that alkyl replaces.

In some respects, hydrocarbyl oxycarbonyl based compound can be for having the polyalkylene succinyl oxide reagent of following formula:

R wherein ²for hydrocarbyl portion, for example, there is the polyalkenyl group of approximately 100 to approximately 5,000 number-average molecular weights.For example, by GPC, measure R ²number-average molecular weight can be approximately 200 to approximately 3,000 dalton.Except as otherwise noted, the molecular weight in this specification sheets is number-average molecular weight.

R ²polyalkenyl group can comprise one or more polymer units linear or branching thiazolinyl unit that are selected from.In some respects, thiazolinyl unit can have approximately 2 to approximately 10 carbon atoms.For example, polyalkenyl group can comprise one or more linear or branched polymer unit that are selected from ethylidene group, propylidene group, butylidene group, pentylidene group, hexylidene group, octylene group and sub-decyl group.In some respects, R ²polyalkenyl group can be for example form of homopolymer, multipolymer or terpolymer.In one aspect, polyalkenyl group is isobutylene.For example, polyalkenyl group can be the homopolymer of polyisobutene, comprises approximately 10 to approximately 60 isobutylenes, for example approximately 20 to approximately 30 isobutylenes.Be used for generating R ²the polyalkenyl compound of polyalkenyl group can generate by any applicable method, and for example, the conventional catalytic oligomerization by alkene reacts.

In yet another aspect, hydrocarbyl portion R ²can be derived from the linear alhpa olefin by preparing in the ethylene oligomerization reaction of method well known in the art or acid isomer alhpa olefin.These hydrocarbyl portions can have approximately 8 carbon atoms to surpassing 40 carbon atoms.For example, the alkenyl part of this type can be derived from linear C ₁₈alhpa olefin or C _20-24the mixture of alhpa olefin or derived from acid isomer C ₁₆alhpa olefin.

In some respects, the available highly reactive polyisobutenes with the polymer molecule of relatively a high proportion of tool terminal vinylidene generates R ²group.In an example, polyisobutene for example, comprises end olefinic double bond at least about 60% (, approximately 70% to approximately 90%).Industrial, generally trend towards changing into highly reactive polyisobutenes, the highly reactive polyisobutenes of knowing is disclosed in for example U.S. Patent number 4,152,499, and its disclosure is incorporated herein by reference in full.

The specific examples of hydrocarbyl oxycarbonyl based compound comprises for example dodecenyl succinic anhydride, C _16-18the compound of alkenyl succinic anhydride and polyisobutenyl succinic anhydride (PIBSA).In some embodiments, PIBSA can have vinylidene content approximately 4% to the polyisobutene part that is greater than approximately 90%.In some embodiments, in hydrocarbyl oxycarbonyl based compound, carbonyl number can be about 1:1 to about 6:1 with the ratio of hydrocarbyl portion number.

In some respects, can react approximately 1 mole of maleic anhydride by every mole of polyalkylene, make the polyalkylene succinyl oxide obtaining there is approximately 0.8 to approximately 1 succinyl oxide base of each polyalkylene substituting group.In other side, the weight ratio of succinic anhydride group and alkylidene group approximately 0.5 to approximately 3.5 scope, for example, approximately 1 to approximately 1.1.

Hydrocarbyl oxycarbonyl based compound can be prepared with any appropriate methodology.Generate the method for hydrocarbyl oxycarbonyl based compound well known.An example that generates the currently known methods of hydrocarbyl oxycarbonyl based compound comprises fusion polyolefine and maleic anhydride.Polyolefine and maleic anhydride reagent are heated to for example temperature of approximately 150 ℃ to approximately 250 ℃, optionally use catalyzer, for example chlorine or superoxide.The another kind of illustrative methods of preparing polyalkylene succinyl oxide is described in U.S. Patent number 4,234,435, and described full patent texts is incorporated herein by reference.

Above-mentioned hydrocarbyl oxycarbonyl based compound and amine compound can be mixed together under the condition of being applicable to, so that required product amino-triazole compound thing of the present disclosure to be provided.Aspect one of the present disclosure, can about 1:1 reaction agent compounds be mixed together to the alkyl carbonyl of about 1:2.5 and the mol ratio of amine.For example, the mol ratio of reagent can be for about 1:1 be to about 1:2.2.

At barometric point, applicable temperature of reaction can be approximately 155 ℃ to approximately 200 ℃.For example, temperature of reaction can be approximately 160 ℃ to approximately 190 ℃.Can use any applicable reaction pressure, for example, comprise lower than atmospheric pressure or superatmospheric pressure.Yet temperature range can be different from those that list when normal atmosphere pressure in addition reacts.Reaction can be carried out approximately 1 hour to approximately 8 hours sections, preferably in the scope of approximately 2 hours to approximately 6 hours.

Aspect more of the present disclosure, compound (A) can be used in combination with diesel oil fuel soluble carrier.These carriers can be all kinds, as liquid or solid, and wax for example.The example of liquid vehicle includes but not limited to mineral oil and oxygenatedchemicals (oxygenate), for example liquid poly-alkoxylation ether (also referred to as polyalkylene glycol or polyalkylene ether), liquid poly-alkoxylation phenol, liquid poly-alkoxylation ester, liquid poly-alkoxylation amine, and composition thereof.The example of oxygenatedchemicals carrier can be found in the U.S. Patent number 5,752,989 of authorizing Henly etc. on May 19th, 1998, and the explanation of those carriers is all incorporated herein by reference.The other example of oxygenatedchemicals carrier comprises the aryl poly-alkoxylation thing that alkyl replaces, and described in the U.S. Patent Publication of the Colucci announcing on July 17th, 2003 etc. number 2003/0131527, its explanation is incorporated herein by reference in full.

In other respects, composition of the present disclosure can not contain carrier.For example, the application's some compositions can not contain mineral oil or oxygenatedchemicals, those oxygenatedchemicalss as previously discussed.

In the fuel composition of disclosed embodiment, can there are one or more other optional compound.For example, fuel can comprise cetane number improver, corrosion inhibitor, cold flow improver (CFPP additive), pour point reducer, solvent, demulsifying compound, slip additive, friction modifiers, amine stabiliser, combustion improving agent, dispersion agent, antioxidant, thermo-stabilizer, conductivity improving agent, metal passivator, labeling dye, organic nitrates ignition accelerator, cyclopentadienyl tricarbonyl manganese compound (cyclomatic manganese tricarbonyl) of convention amount etc.In some respects, composition described herein can comprise based on one or more of multifunctional additive for lubricating oils gross weight approximately 10% weight or above additive still less, or in other side, approximately 5% weight or still less.Similarly, fuel can comprise the conventional oil blending compound of suitable amount, such as methyl alcohol, ethanol, dialkyl ether etc.

Aspect some of disclosed embodiment, can use organic nitrates ignition accelerator, comprise that wherein aliphatic series or alicyclic group are saturated aliphatic series or alicyclic nitric ether, and comprise approximately 12 carbon atoms at most.The example of spendable organic nitrates ignition accelerator is methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, nitric acid allyl ester, nitric acid butyl ester, isobutyl nitrate, the secondary butyl ester of nitric acid, the nitric acid tert-butyl ester, amyl nitrate, isoamyl nitrate, 1-Methylbutyl nitrate, nitric acid 3-pentyl ester, the own ester of nitric acid, nitric acid heptyl ester, nitric acid 2-heptyl ester, n-octyl nitrate, isooctyl ester nitrate, nitric acid 2-ethylhexyl, nitric acid ester in the ninth of the ten Heavenly Stems, decyl nitrate, nitric acid undecyl ester, nitric acid dodecyl ester, nitric acid ring pentyl ester, cyclohexyl nitrate, nitric acid methyl cyclohexyl, nitric acid cyclo-dodecyl ester, nitric acid 2-ethoxy ethyl ester, nitric acid 2-(2-ethoxy ethoxy) ethyl ester, nitric acid tetrahydrofuran base ester etc.Also can use the mixture of this class material.

The example of applicable optional metals passivator that can be used for the application's composition is disclosed in the U.S. Patent number 4,482,357 of promulgating on November 13rd, 1984, and its disclosure is incorporated herein by reference in full.This metalloid passivator comprises for example salicylidene Ortho-Aminophenol, Disalicylidene ethylene diamine, two salicylidene propylene diamine and N, N'-bis-salicylidenes-1，2-diaminopropane.

The optional cyclopentadienyl tricarbonyl manganese compound being applicable to that can be used for the application's composition comprises for example cyclopentadienyl tricarbonyl manganese, methyl cyclopentadienyl tricarbonyl manganese, indenyl manganese tricarbonyl and ethyl cyclopentadienyl tricarbonyl manganese.Other example of applicable cyclopentadienyl tricarbonyl manganese compound is disclosed in the U.S. Patent number 5 of promulgating on November 19th, 1996, the U.S. Patent number 3,015 that on January 2nd, 575,823 and 1962 promulgates, 668, the disclosure of the two is incorporated herein by reference in full.

In one embodiment, fuel composition of the present disclosure can comprise the succinimide dispersants of (B) alkyl replacement and the mixture of said components (A) combination.Term used herein " succinimide " refers to the complete reaction product that comprises the reaction between the amber acid or anhydride (or as succinic acylating agent) replacing from amine and alkyl, and is intended to comprise product wherein except the reaction from amine and anhydride component or contacts the imide bond of the type obtaining also can have the compound of acid amides and/or sat linkage.

By first making the ethylenically unsaturated hydrocarbons of desired molecule amount react with maleic anhydride, can generate the succinyl oxide that applicable alkyl replaces.Can use the temperature of reaction of approximately 100 ℃ to approximately 250 ℃.

Utilize higher ethylenically unsaturated hydrocarbons, can obtain good result at approximately 200 ℃ to approximately 250 ℃.This reaction can promote by chlorination.

General alkene can include but not limited to polymkeric substance and the multipolymer of cracked wax olefin, linear alpha-olefin, branching alpha-olefin, light alkene.Alkene can be selected from ethene, propylene, butylene (for example, iso-butylene), 1-octene, 1-hexene, 1-decene etc.Available polymkeric substance and/or multipolymer can include but not limited to polypropylene, polybutene, polyisobutene, ethylene-propylene copolymer, ethene-isobutylene copolymers, propylene-isobutylene copolymers, ethene-1-decene multipolymer etc.

Aspect of disclosed embodiment, the hydrocarbyl substituent of the succinyl oxide that alkyl replaces can be derived from butene polymers, for example the polymkeric substance of iso-butylene.For applicable polyisobutene herein, comprise from having at least about 60% those polyisobutene that the HR-PIB of the terminal vinylidene content of (for example, approximately 70% to approximately 90% and more than) generates.Applicable polyisobutene can comprise uses BF ₃those polyisobutene prepared by catalyzer.As measured by GPC, the number-average molecular weight of hydrocarbyl substituent can change in wide region, and for example approximately 100 to approximately 5000, approximately 500 to approximately 5000 dalton for example.

Can use beyond maleic anhydride containing carboxyl reaction agent, such as toxilic acid, fumaric acid, oxysuccinic acid, tartrate, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methylfumaric acid, ethyl maleic anhydride, dimethyl maleic anhydride, ethyl toxilic acid, dimethyl maleic acid, hexyl toxilic acid etc., comprises corresponding carboxylic acid halides and rudimentary aliphatic ester.In reaction mixture, the mol ratio of maleic anhydride and alkene can extensively change.Therefore, mol ratio can change to approximately 1.5 from about 5:1, and for example about 3:1, to about 1:3, as another example, can be used the excessive maleic anhydride of stoichiometry, to force, reacts completely.Unreacted maleic anhydride can be removed by vacuum distilling.

In the preparation of the succinimide dispersants that can replace at alkyl, utilize any multiple polyamines.Non-limiting exemplary polyamines can comprise aminoguanidine bicarbonate (AGBC), diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), penten (PEHA) and heavy polyamines.Heavy polyamines can comprise the mixture of polyalkylene polyamine, there is a small amount of rudimentary polyamines oligopolymer (as TEPA and PEHA), but be mainly, have seven or more nitrogen-atoms, two or more primary amine of per molecule and than the oligopolymer of the more substantial branch of conventional polyamine mixture.The other unrestricted polyamines that can be used for preparing the succinimide dispersants that alkyl replaces is disclosed in U.S. Patent number 6,548,458, and its disclosure is incorporated herein by reference in full.In an embodiment of the present disclosure, polyamines can be selected from tetren (TEPA).

In one embodiment, dispersion agent can comprise the compound of following formula:

Wherein n represents 0 or 1 to 5 integer, R ²for the hydrocarbyl substituent being defined as above.In one embodiment, n is 3, R ²for polyisobutenyl substituting group, for example, from having at least about the 60% derivative substituting group of polyisobutene of the terminal vinylidene content of (for example, approximately 70% to approximately 90% and more than).The compound of aforementioned formula can be the succinyl oxide (for example, polyisobutenyl succinic anhydride (PIBSA)) of alkyl replacement and the reaction product of polyamines (for example, tetren (TEPA)).

When preparation the application's fuel composition, can be enough to reduce or suppress the amount that in diesel motor, settling forms and use additive.In some respects, fuel can comprise the above-mentioned bis-amino triazole compounds of controlling or reducing the minor amount that forms engine deposits (for example injector deposits in diesel motor).For example, the application's diesel oil fuel can comprise the bis-amino triazole compounds to the amount of about 500mg bis-amino triazole compounds/Kg fuel based on the about 5mg of activeconstituents benchmark, and for example about 20mg is to about 120mg bis-amino triazole compounds/Kg fuel.Utilize carrier aspect in, fuel composition can comprise the carrier to the amount of about 100mg carrier/Kg fuel based on the about 1mg of activeconstituents benchmark, for example about 5mg is to about 50mg dispersion agent/Kg fuel.Activeconstituents benchmark does not comprise the weight of following material: (i) in conjunction with and be retained in preparation and the product that uses in unreacted components, for example, polyalkylene compound; (ii) in bis-amino triazole compounds preparation, during it forms or afterwards but the solvent that before adding carrier, (if utilizing carrier) used (if existence).

On the other hand, fuel composition of the present disclosure can comprise the dispersion agent as herein described (B) based on activeconstituents benchmark approximately 50 amounts to about 500ppm, for example based on the about 80ppm of fuel composition gross weight to about 200ppm (weight).

Utilize carrier aspect, fuel composition can comprise the carrier to the amount of about 1000mg carrier/Kg fuel based on the about 10mg of activeconstituents benchmark, for example about 25mg is to about 700mg carrier/Kg fuel.Activeconstituents benchmark does not comprise the weight of following material: (i) in conjunction with and be retained in preparation and the disclosed additive that uses in unreacted components; (ii) in the preparation of disclosed additive during it forms or afterwards but the solvent that before adding carrier, (if utilizing carrier) used (if existence).

The application's additive, comprises above-mentioned bis-amino triazole compounds and the optional additive using in fuel preparation of the present invention, can mix base diesel fuel separately or with various sub-portfolios.In some embodiments, the application's binder component useful additives enriched material mixes diesel oil fuel simultaneously, because while being multifunctional additive for lubricating oils form, and mutual consistency and facility that this has utilized the combination by composition to provide.Use enriched material also can reduce blending time, and reduce the possibility of fusion mistake.

Therefore, in certain embodiments, the application relates to a kind of diesel fuel additive, and described diesel fuel additive comprises bis-amino triazole compounds, and this compound is the reaction product of above-mentioned at least one guanidine and at least one polyalkylene succinyl oxide.Additive can comprise one or more of above listed other composition.Additive can, through packing, and separate and sell with diesel oil fuel with for example enriched material form.Then, can be by client as required by additive and diesel oil fuel fusion.

The application's diesel oil fuel (for example can be used for fixedly diesel motor, engine for power generating equipment, pumping plant etc.) and both operations of on-fixed diesel motor (for example, being used as the engine of primover in automobile, truck, the smooth equipment of highway, military vehicle etc.).Therefore, the application's aspect relates to the method for amount of the injector deposits of the diesel motor that reduces the one or more direct fuel injectors have at least one combustion chamber and to be communicated with combustion chamber fluid.In yet another aspect, also can indirectly in diesel fuel injectors, observe improvement.In some respects, method comprises the injector injection combustion chamber of the compression ignition fuel based on hydrocarbon of the bis-amino triazole additive that comprises the application being passed through to diesel motor, and compression ignition fuel is lighted a fire.In some respects, method also can comprise at least one in above-mentioned optional other composition sneaked into diesel oil fuel.

In one embodiment, the application's diesel oil fuel can be substantially for example, containing (completely without) conventional succinimide dispersants compound.According to the application intention, term " substantially containing " is defined as injector degree of cleaning or settling is formed to the concentration that there is no in fact detectable impact.

Aspect another of the application, fuel dope can be not containing or substantially containing 1,2 beyond above-mentioned triazole, 4-triazole.For example, composition can not contain the triazole of formula II substantially,

R wherein ⁴and R ⁵independently be selected from hydrogen and alkyl, its condition is R ⁴and R ⁵be not one of at least hydrogen.The example of alkyl comprises C ₂to C ₅₀linear, branch or cyclic alkyl; C ₂to C ₅₀linear, branch or ring-type thiazolinyl; Be substituted or unsubstituted aryl, for example phenyl, tolyl and xylyl.

Do not wish bound by theory, believe that the inside salt deposit in fuel injector can produce by the metal ion pollution in fuel.Metal ion can be from basic fuel itself, or comes from the additive of putting into basic fuel.While existing, metal ion can (for example, corrosion inhibitor (for example, dodecyl succinate corrosion inhibitor) and/or the reaction of biofuel fatty acid ester, to generate salt type settling with carboxylate salt (ester) sense fuel dope.Because modern injector is manufactured poling close tolerance (extremely close tolerance), any this class settling all seriously the intraware of limit injection device move.Therefore, salt deposit can cause the significance loss of energy owing to clinging injector needle, reduces fuel economy, wasted power and increase discharge.Inside deposition thing is generally not too general in conventional diesel oil fuel, but has found expression in ULSD fuel.Unexpectedly, as described herein, find component (A) separately or cleaned and/or prevented from generating the inner salt deposit of this class with component (B) combination on fuel injector.

Embodiment

Following examples are the explanation of exemplary of the present disclosure.In other place of these embodiment and the application, except as otherwise noted, all umbers and percentage ratio are all by weight.These embodiment are only intended to for illustration purpose provides, and are not intended to limit scope of the present invention disclosed herein.

In following examples, for high pressure co-rail diesel fuel system, the impact on the diesel oil fuel polluting with carboxylate salt of assessing compound (A) and/or the additive that (A) adds (B).The tendency that causes fuel injector adhesion with testing of engine proof fuel, also proves that some fuel dope prevents or control the ability of inside deposition thing in injector.With engine dynamometer testing table, install for moving the Peugeot DW10 diesel motor of injector adherence test.This engine is 2.0 liters of engines with four cylinders.Each combustion chamber has 4 valves, and fuel injector is the DI piezoelectric injector with Euro V classification.

Core rules program is by forming below: make engine operation by circulation in 8 hours, and allow engine soaking (soak) (tail-off) specified time measure.Then, for each cylinder, by measuring cylinder exhaust gas thermometer, levy injector performance.If point at any time, the exhaust temperature of any cylinder surpasses 65 ℃ higher than any other cylinder exhaust temperature, just stops test, and thinks fault (one or more injector adhesion).If allowing engine cool after envrionment temperature, cold start-up shows 45 ℃ or larger temperature contrast in cylinder exhaust temperature, also thinks and tests fault.Can also determine that pin is removed to required power from nozzle housing to be confirmed the adhesion of pin and confirm thus fault by taking injector subjectivity apart.For performance and the test of clean-up performance operation degree of cleaning of keeping clean.

Test prepares to comprise the fuel from testing before engine rinses, and removes afterwards injector.Check test injector, cleans, and is reinstalled in engine.If select new injector, make new injector circulate by break-in in 16 hours.Then, with required testing campaign program starting engine.Once engine gets hotter, just detection power under 4000RPM and full load, recovers for the full power after clean injector.If power detection result, in specification, just starts testing campaign.Following table 1 is provided for evaluating the performance according to the DW10 adherence test circulation of fuel dope of the present disclosure.

performance in 1 hour of table 1-DW10 adherence test circulation.

Step	Time length (minute)	Engine speed (rpm)	Load (%)	Moment of torsion (Nm)	Forced air after charge air cooler (℃)
						1	2	1750	20	62	45
2	7	3000	60	173	50
						3	2	1750	20	62	45
4	7	3500	80	212	50
						5	2	1750	20	62	45
6	10	4000	100	*	50
						7	2	1250	10	25	43
8	7	3000	100	*	50
						9	2	1250	10	25	43
10	10	2000	100	*	50
						11	2	1250	10	25	43
12	7	4000	100	*	50

embodiment 1 (injector adhesion testing of engine)

Diesel motor nozzle adherence test is carried out according to the rules of table 1 with Peugeot DW10 engine.For the test that keeps clean, the diesel oil fuel polluting with metal carboxylate is also used in the detergent additive operation engine of indicating in embodiment.For cleaner assay, first with the diesel oil fuel of metal carboxylate pollution, without detergent additive, move engine, to set up the baseline of adhesion fuel injector.Then, with the equal fuel operation engine of detergent additive shown in comprising.In all tests, the fuel package of test is containing 200ppmv oilness properties-correcting agent and 1600ppmv cetane number improver, 20ppmw dodecyl succinate, 3ppmw NaOH and 25ppmwv water.In on-test, for all 4 cylinders, as shown in (Fig. 1), exhaust temperature indication does not uniformly have injector adhesion.Yet, in the cold start-up of 8 hours rear engines, show injector adhesion, as shown in Figure 2.In all figure, curve A is cylinder 1, and curve B is cylinder 2, and curve C is cylinder 3, and curve D is cylinder 4.

comparing embodiment 2

In this embodiment, conventional succinimide dispersant additives is added to fuel with 75ppmw treatment rate.Fig. 3 shows with injector adhesion after the test in 16 hours of the fuel containing conventional sanitising agent.

comparing embodiment 3

In this embodiment, quaternary ammonium salt diesel fuel additive suit is added to fuel with 75ppmw treatment rate.Fig. 4 shows with injector adhesion after the test in 7 hours of this fuel.

embodiment 4

Compound (A) is added to fuel with 75ppmw treatment rate.After test in 16 hours, Fig. 5 shows all not adhesions of injector.Physical examination injector after test completes, determines all not adhesions of injector.

embodiment 5

In this test, for the total treatment rate of 75ppmw, compound (B) combination by the compound of 15ppmw (A) with 60ppmw.After Fig. 6 is presented at test in 16 hours, injector is not all adhered.

embodiment 6

In this test, prove the ability of the clean dirty fuel injector of detergent additive.Total treatment rate of 50ppmw in for fuel, before adding the mixture of the compound (A) of 10ppmw and the compound (B) of 40ppmw, dirty fuel injector has the exhaust temperature that is similar to Fig. 2.After Fig. 7 is presented at test in 8 hours, injector is not all adhered.

As shown in the previous embodiment, with the comparison of conventional oil detergent additive, when with ULSD operating fuel engine, inclusion compound (A) or compound (A) add that the fuel dope of compound (B) significantly reduces the inside deposition thing in diesel fuel injectors.

It should be noted that, as used in this specification sheets and accessory claim, singulative " ", " being somebody's turn to do " and " described " comprise plural indicator, unless specially and be clearly limited to an indicator.Term used herein " comprises " and grammatical variants is intended to for non-limiting, makes not get rid of other similar items that can replace or be added to cited project in the narration of enumerating middle project.

For the intention of this specification sheets and additional claims, except as otherwise noted, the numeral of all expression amounts, percentage ratio or ratio and other numerical value using in specification sheets and claim is all interpreted as being subject in all cases word " approximately " to modify.Therefore, unless be indicated as being on the contrary, the digital parameters of listing in specification sheets and accessory claim is approximation, can change according to the desired properties of seeking by the disclosure to obtain.At bottom line, and not as attempting the application of restriction to the doctrine of equivalents of claim scope, each digital parameters should be at least according to the numerical value of reported significant figure and by using common rounding method to make an explanation.

Although described specific embodiments, applicant or those skilled in the art can make and not predict at present or may at present unforeseenly substitute, modification, variation, improvement and essentially equivalent thing.Therefore, submission be intended to comprise with revisable accessory claim that all these substitute, modification, variation, improvement and essentially equivalent thing.

Claims (10)

1. the method cleaning for the intraware of the fuel injector of diesel motor, described method comprises with a kind of fuel composition operation fuel injection diesel motor, the fuel that described fuel composition comprises main amount and the compound to (A) following formula of about 500ppm weight based on fuel composition gross weight approximately 10:

And tautomer and enantiomer, wherein R ²for thering is the alkyl of 100 to 5000 daltons number average molecular weight.

2. the process of claim 1 wherein that fuel injection diesel motor comprises that direct fuel sprays diesel motor.

3. the method for claim 1, further comprises (B) a certain amount of hydrocarbyl succinic imide dispersion agent, and wherein in fuel, the weight ratio of A:B is 1:2 to 1:10.

4. the method for claim 3, the reaction product that wherein hydrocarbyl succinic imide dispersion agent comprises polyalkenyl amber acid or anhydride and tetren, wherein polyalkenyl amber acid or anhydride is derived from the polyisobutene with 800 to 1100 daltons number average molecular weight, and wherein polyisobutene comprises the highly reactive polyisobutenes with at least 70% weight or more end olefinic double bonds.

5. the method for claim 3, wherein fuel package is containing 50 to the 500ppm A of weight and the mixture of B.

6. the method for the amount of the minimizing salt deposit on the intraware of the fuel injector for fuel injection diesel motor, described method comprises with a kind of fuel composition operation diesel motor, the compound of (A) following formula of the fuel that described fuel composition comprises main amount and minor amount:

And tautomer and enantiomer, wherein R ²for thering is the alkyl of 100 to 5000 number-average molecular weights.

7. the method for claim 6, wherein R ²for thering are approximately 200 alkyl to approximately 3000 daltons number average molecular weight.

8. the method for claim 6, wherein fuel is ultra-low-sulphur diesel fuel.

9. the method for claim 6, further comprise (B) a certain amount of hydrocarbyl succinic imide dispersion agent, wherein in fuel, the weight ratio of A:B is 1:2 to 1:10, the reaction product that wherein hydrocarbyl succinic imide dispersion agent comprises polyalkenyl amber acid or anhydride and tetren.

10. prevent the method that the fuel filter for the fuel injector of fuel injection diesel motor stops up, described method comprises following (A) and the mixture (B) that the fuel of main amount and minor amount are provided: (A) compound of following formula

And tautomer and enantiomer, wherein R ²for thering is the alkyl of 100 to 5000 daltons number average molecular weight; (B) a certain amount of hydrocarbyl succinic imide dispersion agent; Wherein in fuel, the weight ratio of A:B is 1:2 to 1:10; And

Make fuel flow pass through the fuel filter for fuel injector.

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